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Proceedings of the Chemical Society, Vol. 10, No. 145 |
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Proceedings of the Chemical Society, London,
Volume 10,
Issue 145,
1894,
Page 235-242
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摘要:
Issued 11/1/1893 PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 145. Session 1894-95. December 20th, 1894. Dr. Armstrong, President, in the Chair. Messrs. Claude Smith and Frederick J.Allen were formally admitted Fellows of tlie Society. Certificates were read for t'he first time in favour of Messrs, Herbert Anderson? County School, Wellington, Someixet ; Francis H. Carr, Meaburne, Warham Road, Croydon ; Donald St. John Grant, M.A., M.B., Lahore, India; Herbert Grime, 11, Church Road, Chorl- ton-cum-Hardy, Manchester ; John Adnms Hatfield, 89, Bridge Street, W'ednesbury ; Percy Hndson, 48, Alexandra Road, Barton-on-Trent ; Patrick Henry Kirkaldy, 68, East India Road, Poplar, E. ; William Baxter McVey, 301, Snratoga Street, Boston, Mass.; Herbert Frederick Stephenson, 10, Muschamp Ittoad, E.Dnlwich, S.E.; Thomas C. Warington, 1, Charles Street, Hanley, Stsffordshire ; Henry Stow Young, 13, Balham Grove, S.W. The following is the text of an address which has been sent to Professor C. Remigius Fresenins, who has now been fifty years a Foreign Member of the Society :-" Geh. Hofrath Professor Dr. C. R. Fresenius, "DEARSIR, " It is little more than two years ago that the Chemical Society addressed its congratulations to Professor Bunsen, its senior Foreign Member, on the 50th anniversary of his election into our body. It is now oar privilege, on behalf of the Fellows, to address you, who come next to him on our list of Foreign Members, on a similar occasion ; and to congratulate you on having so long retained your vigour and pursued your career of nsef ulness in that most important branch of our science, analytical chemistry, the cultivation of which you hare made so especially the work of your life.23G “We rejoice to have your name among those of the early COII-tributors to our journal, communications from you on an improred method for the detection and quantitative determination of arsenic, and on inorganic constituents of plants, appearing in the second voIume of our Memoirs. Indeed, you were elected into our Society at a time when it was customary to choose as Foreign Members only those chemists abroad who had become directly and intimately connected with us by contributing to our Proceedings, your name coming very early on a list of such contributors at the head of which are the names of Liebig and Bunsen.‘‘ There are still some among us who knew you as a student ; not a few also who have been students under you ; but you are also well known to the Fellows generally, all of whom, indeed, feel that they owe you much gratitude for the assistance that you have afforded them, both in their studies and in their professional work, through your invaluable text-books on qualitative and quantitative analysis, and through the ‘Zeitschrift’ you have so long conducted, which renders such signal service to chemists by keeping them informed of the progress of analytical chemistry. “On behalf of English chemists generally, we have to express the earnest wish that you may be permitted during many years to come to continue to carry on labours which are so generally appreciated.” H.E. ARMSTRONG,.President ;T. E. TrIomE, Treasui-er. J. M. THOMSON, R. DUNSTAN,WYXDHAN Secretaries. R.MELDOLA,E’oreiglz Sewetnry. Of the following papers those marked * were read. “81. “An improved form of barometer.” By J. Norman Collie, Ph.D. In the improved form of barometer described by the author, several new devices are introduced. Lightness and strength are secured by using for the stem of the instrument thick Spyengel pump tubing. The upper and lower part of the barometer is made from the same piece of tubing, so that the diameter of the cisterns is the same throughout. Just below theupper cistern a small glass trap is inserted, to pre-vent air which may creep tip the stem from entering the Torricellian vacuuni.The mercury in the lower cistern is connected with the upper part of the barometer by means of a small tube of capillary bore. This capillary tube is bent just below the point of junction with the bottom of the Sprengel tube, so as to lie along the inner wall of the lower cistern ; by tliis means an unobstructed view of the top of the mercury at the lower level is obtained. The scale may be etched either on the barometer itself or on a thick plate glass mirror, which is placed behind the instrument. Very accurate readings are thus obtained. P3i Jh. C. E. SIiiller has suggested a further improvement in the form nf a ground-glass joint inserted in the middle of the barometer.This renders the instrument easier to fill and clean, besides allowing of its being packed in a box of convenient form. ”82. “The Constituents of Piper Ovatum.” By Wyndham R. Dunstan, F.R.S., and Henry Gamett. This is a West Indian medicinal plant growing in Trinidad. When chewed it gives rise to a tingling sensation and profusc salivation, accompanied by temporary local anesthesia. The leaves were found to contain a terpene, and a considerable quantity of physiologically active resin, which is also present in the root and stems. Froin this “ resin ” the authors were ultimately able, by a tedious process, to separate a crystalline highly active substance, which they name p+eroz.atine.Its composition is expressed by the formula C16H21N02, and it appears to possess an alkaloidal structure, but is, nerertheless, devoid of basic properties. It is nearly insoluble in water and in dilute acid and alkalis, but dissolves readily in alcohol, and the alco- holicsolution exhibits the curious property of setting to a “jelly ” of very minute crystals when water is added to it. Piperovatine acts as a temporary depressant of both motor and sensory nerves, and also as a heart poison. It p~oducesa powerful stimulant effect on the spinal cord, causing a tonic spasm resembling that of stzyclinine. It, seems likely to be of service in therapeutics. “83.“Note on the active constituent of the Pellitory of medicine.” ByWyndham R. Dunstan, F.R.S.,and Henry Gamett.The similarity in the physiological effect produced by Piper Ovatum and by the Pellitory of medicine (AnacycZus pyrethrum), led the authors to examine this plant, the activity of which is usually ascribed to a resin. The authors have separated from this resin a crystalline, intensely active substance which they name peblitorine. In most of its chemical and physical properties it closely resembles piperovatine ; but so far it has always exhibited certain small dif- ferences which may possibly disappear when the substance has been further purified. Both piperovatine and pellitorine appear to be pyridine derivatives, but neither possesses any appreciable basic power. “84. “The determination of some high temperature freezing points by means of platinum-resistance pyrometers.” By C.T. Heycock and F. H. Neville. From time to time the authors have communicated to the Society the results of experiments on the freezing points of alloys in which 238 sodium, tin, bismuth, cadmium, thallium, and lead were the solvent metals. These experiments have now been extended to temperatures above those in which a mercury thermometer could be used by means of a platinum-rcsistance pyrometer. The results, recorded to the nearest whole number, are as follows. Freezing point. Zinc ........................ 419°C. Antimony ................... 624 .. Magnesium.. ................ 633 .. Aluminium .................. 653 .. Silver ...................... 957 ..Copper ..................... 1081 .. Sodium carbonate ............ 848 .. Sodium sulphate ............. 883 .. Potassium sulphate. .......... 1066 .. In making an experiment the pyrometer is plunged into a mass of the molten substance well above its melting point, and the falling temperature is followed until it suddenly stops. This temperature is the freezing point. In the apparatus employed the temperature of freezing is maintained for a minute or more, and after this a fall is obtained which at first is very slow. If the pyrometer is now withdrawn it is found to have a very considerable quantity of solid substance adhering to it. DISCLXSION. Mi. GOWLANDcalled attention to the fact that the metals experi- mented on were not examined for impurities, although care had been taken to procure them as nearly pure as possible from manufacturers.Zinc ae met with in commerce always contains considerable amounts of lead. In some specimens only 0.4 per cent. is present, but in others as much as 1.9 per cent., and even more, is occasionally found. Zinc also contains cadmium, and this is especially the case in the . so-called " pure " redistilled metal. Whilst investigating 8 method for the determination of antimony in copper by the nature of the fracture of one of its alloys with zinc, he had noticed that ordinary zinc (spelter) gave satisfactory results, but when so-called " piire " zinc which had been redistilled by the manufacturer was used, the results were altogether anomalous.On examining this zinc, it was found to be contaminated with cadmium, two cakes containing 5.2 per cent., another about 3 per cent., and a fourth little more than traces. In the case of copper, commercial samples vary much iu the pro- portions of metallic impurities and of suboxide present. Even electro- type copper is sometimes impure ; copper should therefore always 239 be tested, the simplest method being a determination of its electric conductivity, as this mill generally sufficiently indicate the extent of its purity. Copper when melted, even under a thick layer of charcoal, will absorb oxygen, and become contaminated with sub- oxide. He suggested that it would be desirable in future to ascertain the chief impurities in the metals experimented on, and to determine their amounts, for even when present in small proportions they often have, as is well known, marked effects on the physical properties.This would add very greatly to the value of the determinations of their freezing points, and would enable them to be compared with the results obtained by other observers. *85. "The preparation of adipic acid and some of its derivatives." By Walter H. Ince, Ph.D. Wislicenns's method o€ preparing adipic acid by heating /3-iodo-propionic acid wit,h silver being found to be unsatisfactory, other iiiethods of preparation were investigated. According to Arppe (Zeit. f. Chem., lS65, 300), adipic acid may be readily prepared by the action of nitric acid on ssbecic acid.The author finds, however, that not only has nitric acid no action on sebacic acid, but th;it sebacic acid crystallises unchanged from its solution in fuming nitric acid. By the action of potassium per-nianganate in neutral, acid, and alkaline solutions sebacic acid is entirely decomposed, yielding small quantities of a monobasic acid, but no adipic acid. Malaguti (Am. Chim. Phys., C33, 16, 84) states that when beef suet is heated with ordinary nitric acid, the main product is adipic acid. The author in repeating the experiment finds that when ordinary nitric acid is used, the ma.in product consists of sebacic and azela'ic acids, and, when fuming nitric acid is used, an acid having the formula C11H2,04is among the products.In neither case could the presence of adipic acid be detected. As might be anticipated, the action of nitric acid on bee€ suet is a complex one, and the products vary with the concentration of the acid employed : but in no case does adipic acid appear to be formed. ~~ a-JIonob?.omadipic acid, (? H2*CH,*COOH was prepared by Gal CH2*CH*Br*cooH, and Gay-Lussac (Annalen, 155, 250), but was not obtained in a pure state. The author has isoIated it in a state of purity by hcating ndipic acid (1mol. prop,) with bromine (2 mol. props.) in a sealed t,ube at 160" for two hours. The semiorystalline contents of the tube are dissolved in ether, and yield on recrystallisation from abso- Jute alcohol, small colourless crystals melting at 131". When mixed 240 with water or a dilute solution of potassium hydroxide, this acid readily changes into a-hydrozyadipic acid, CJX,OH(COOH),.This is extracted from the aqueous solution by ether, which on evapora- tion deposits colourless crystals melting at 151", and subliming mith- out decomposition, This acid is soluble in alcohol, water, arid sether. "86. "The action of hydrogen chloride on the oxides of calcium, barium, and magnesium." By V. H. Veley, F.R.S. In continuation of former experiments (Trans., 1893 and 1894), the author finds that dry hydrogen chloride does not act on quick-lime at ordinary temperatures, or at 40", but at 80" action occurs. Dry hydrogen chloride does not act on magnesia at ordinary teni- peratures; at 40°, however, action takes place to a considerable extent.Dry hydrogen chloride was observed to attack baryta at all temperatures. DISCCSSTON. The PRESIDENTexpressed the opinion that our knowledge of the conditions wliieh determine chemical change, and of the influence of water, was now such that it was necessary to adopt every possible precaution in preparing dry materials, and that the mere passage of a gas over a drying agent was not sufficient. He thought that on this account Mr. Veley's results were entirely inconclusive, and that the enquiry ought to have been carried further before an attempt was made to state coiiclusions. It was to be expected that barium oxide would be more easily acted on, as baryta was dehydrated less readily than lime or magnesia.*87.'' Latent heat of fusion." By Holland Crompton. If the latent heat of fusion of a, unit weight of a metal is multiplied by the atomic weight of the element and divided by the absolute temperature of fusion, the resulting quantity is proportional to the valency of the metal, or in other words equivalent quantities of the metallic elements undergo on fusion equal changes in entropy. 111 modified form this rule is found to hold also fcr the non-metals. In the case of compounds, the molecnlar latent heat of fusioii divided by the absolute temperature of fusion is also proportional to the sum of the valencies of the atoms composing the molecule. 'It is necessary, however, in this case to suppose that the valencies are to a certain extent influenced by the mode of union of the atoms with one another., and modified in accordance with certain definite empirical rules stated by the author.For elements, therefore, the relationship wA/Tv = 1.38, and for compounds the similar relationship w;\I/TXv = 1-38is found to hold. 241 2c-is the latent heat of unit weight, A the atomic and &f the molecular weight, T is the absolute temperature of fusion, and v and Zr are the rxlencies and the sum of the valencies respectively. By combining these expressions with van’t HOE’S formula for the molecular depression of the fusing point, E = 0.02T2/w,it is possible to calculate the molecular depressioii froin the values of v and T. The numbers thus calculated are compared with those obtained by direct. measurement and found to be in fair agreement.Solubilities OY the melting points of mixtures of known composition can also be calculated, making use of the formula given by Schroder (Zeit. physikal. Chem., 11,449)) connecting the solubility with the latenb hpat of fusion and melting point in absolute temperature. Here, again, agreement between the calculated and observed values is obtained. The relationship enunciated in the papel. throws a new light, ou the question of the mecha,nistii of the change from the solid to the liquid condition. It indicates that this change is one in which the simple chemical molecules and the atoms composing them are mainly concerned, and that, it does not consist merely in the transition of complicated to simpler molecular aggregates.88. ‘‘Metallic tartrarsenites.” By G. G. Henderson, D.Sc., M.A., and A. R.Ewing, Ph.D. Arsenious oxide dissolves readily in hot solutions of sodium hydro-gen tartrate, and when the liquid is concentrated and cooled, colour- 1ess, prismatic crystals of sodium tnrtmrsenite, C*HkO6AsONa*28H20, separate. This is a stnbIe salt, easily soluble in water, butl insoluble in alcohol. The aqueous solution has an acid reaction, and when neutralised with soda gives a mixture of arsenious oxide and disodium tartrate. The corresponding aininoniwn salt resembles the sodium salt, hut is more unstable, gradually decomposing, even in the solid state, into arsenious oxide and ammonium hydrogen tartrate.Potassium tartmrsenite is at once decomposed by cold water, and hence is prepared with greater difficulty. It is obtained as a: finely crystalline precipitate. The charact1eristic barium salt, (CiH406AsO)2Ba*H,0, is prepared in the form of delicate lustrous needles by mixing dilute solutions of barium chloride and of the. sodium salt. It is only slightly soluble in hot water, and is partially decomposed when boiled with much water, like all the salts of the series hitherto examined. The strodunz and calciunz salts are more soluble, and much less stable in solution. The heavy metals give precipitates wit,h soluble tartrarsenites, but these precipitates appear to be in most cases either tart.iates or mixtures of tartrates with arsexious oxide.242 When the barium salt is cautiously niixed with dilute sulphuric acid, keeping the salt in excess, a clear filtrate is obtained, which has a stmng acid reaction, but contains no sulphuric acid, aad which gives a copious precipitate of arsenious sulphide when hydrogen sulphide is added. The solution probably contains free tartrarsenious acid, C,H,06AsOH,but this is too unstable to be isolated. Concen-tration of the solution, or raising its temperature to 60-70°, or addi-tion of alcohol or of a trace of a mineral acid, causes decomposition of the acid i2to arsenions oxide and tartaric acid ;but if soda is added, sodium tartrarsenite is formed, and a quantitative examination OF the solution proved it to contain almost exactly the theoretical quan- tity of arsenic.Experiments with other acid oxides and hydoxy-acids indicate that tartrarsenions acid is either a derivative of arsenious acid, As<:E‘*‘, or an ethereal derivative of tartaric acid, hahing the formula CO2H*CHO(AsO).CH0H*CO2H. 89. ‘‘Note on the interaction of hydrogen sulphide and .bismuth haloid compounds.” By M. M. Pattison Muir, M.A., and Edwin M. Eagles, B.A. The authors find that bismuth chloride and hydrogen sulphicle react at a, very moderate temperature, producing bismuth thiochloride, BiSC1, and hydrogen chloiaide ; that a similar action occurs between bismuth bromide and hydrogen sulphide ; but that bismuth iodide and hydrogen sulphide do not interact. They also prove that bismuth sul-phide is produced by the interaction of bismuth chloride, or bromide and hydrogen sulphide at a red heat.The thiohaloid compounds BiSCf and BiSBr are also formed very readily by passing chlorine 01-hromine vapour- over bismuth sulphide. Bismuth thioiodide was obtained, but not quite free from bismuth sulphide, by heating bis- muth sulphide with bismuth iodide. ERRATUMin :‘ Proceedings,” No. 1&, p. 226. Between lices 11and 13 insert “ DISCUSSION.” At the next meeting, on Thursday, January 17th, the following papers will be read :-“Acid sulphate of hydroxylamine.” By Dr. Divers, F.R8.S. “ Mercury and bismuth hypophosphites.” . By S. Hada. *‘ Karnala.” Part 111. By A. G. Perkin. HABBISOSASD SOIVS,Printers in Ordinary to Her Majesty, St. Martin’6 Lnnc..
ISSN:0369-8718
DOI:10.1039/PL8941000235
出版商:RSC
年代:1894
数据来源: RSC
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